Photoresist compositions and methods

ABSTRACT

New photoresist and topcoat compositions are provided that are useful in a variety of applications. In one aspect, new photoresist compositions are provided that comprise: (a) a first matrix polymer; (b) one or more acid generators; and (c) one or more additive compounds of Formulae (I) and/or (II).

BACKGROUND

The invention relates generally to the manufacture of electronic devices. More specifically, this invention relates to photoresist and topcoat compositions and to photolithographic processes which allow for the formation of fine patterns. Compositions of the invention are particularly useful in immersion lithography processes for the formation of semiconductor devices.

Photoresists are photosensitive films used for the transfer of images to a substrate. A coating layer of a photoresist is formed on a substrate and the photoresist layer is then exposed through a photomask to a source of activating radiation. Following exposure, the photoresist is developed to provide a relief image that permits selective processing of a substrate.

Considerable effort has been made to extend the practical resolution capabilities of positive tone resist development, including in immersion lithography. One such example involves negative tone development (NTD) of a traditionally positive-type chemically amplified photoresist through use of particular developers, typically organic developers such as ketones, esters or ethers, leaving behind a pattern created by the insoluble exposed regions. See, for instance, U.S. Pat. No. 6,790,579.

Certain additives have been employed to attempt to improve resist resolution. See JPH11337722A; US2007190451; EP1702962B1; US20060172149; US20130177853; US20130344436; US20140038102; U.S. Pat. No. 6,132,931; US20120077120; U.S. Pat. Nos. 6,391,521; 9,563,123.

In immersion lithography, direct contact between the immersion fluid and photoresist layer can result in leaching of components of the photoresist into the immersion fluid. This leaching can cause contamination of the optical lens and bring about a change in the effective refractive index and transmission properties of the immersion fluid. In an effort to ameliorate this problem, use of a topcoat layer over the photoresist layer as a harrier between the immersion fluid and underlying photoresist layer has been proposed. The use of topcoat layers in immersion lithography, however, presents various challenges. Topcoat layers can affect, for example, the process window, critical dimension (CD) variation and resist profile depending on characteristics such as topcoat refractive index, thickness, acidity, chemical interaction with the resist and soaking time. In addition, use of a topcoat layer can negatively impact device yield due, for example, to micro-bridging defects which prevent proper resist pattern formation.

To improve performance of topcoat materials, the use of self-segregating topcoat compositions to form a graded topcoat layer has been proposed, for example, in Self-segregating Materials for Immersion Lithography, Daniel P. Sanders et al, Advances in Resist Materials and Processing Technology XXV, Proceedings of the SPIE, Vol 6923, pp. 692309-1-692309-12 (2008). See also US20120264053.

Electronic device manufacturers continually seek increased resolution of a patterned photoresist image. It would be desirable to have new compositions that could provide enhanced imaging capabilities.

SUMMARY

We now provide new compositions that are useful in photolithographic applications, including immersion lithography processes.

In preferred embodiments, the present compositions can exhibit enhanced shelf-life, including comparatively decreased degradation of a composition upon extended storage. See, for instance, the comparative data set forth in the Examples which follow.

More particularly, in a first aspect, photoresist compositions are provided that comprise: (a) a first matrix polymer; (b) one or more acid generators; and (c) one or more additive compounds having a structure of the following Formulae (I) or (II):

wherein in each of those Formulae (I) and (2) R₁ and R₂ are each the same or different non-hydrogen substituent such as optionally substituted alkyl, optionally substituted alkoxy, optionally substituted thioalkyl, optionally substituted carbocyclic aryl or an optionally substituted heteroaromatic group,

or R₁ or R₂ can be connected via a group Z where Z is a single bond or a group selected from C═O; S(O); S(O)₂; —C(═O)O—; —C(═O)NH—; —C(═O)—C(═O)—; —O—; CHOH; CH₂; S; —B—;

-   -   X in each formulae is one of the following:

wherein R₃ is a non-hydrogen substituent; and

each n is a positive integer of 1 to 5. Preferred optional substitution of R₁ and R₂ include for example substitution by —OY—NO₂, —CF₃—; —C(═O)NHY; —C(═O)—C(═O)—Y; CHOY; CH₂Y; —SY; —B(Y)n; —NHC(═O)Y; —(C═O)OY (with Y being a linear or branched, saturated or unsaturated alkyl group, a fluoro alkane or alkene or alkyne, or carbocyclic aryl or heteroaromatic).

In preferred aspects, the photoresist composition will contain a second polymer distinct from the first polymer. Preferably, such a second polymer will comprise fluoro substitution such as one or more fluoroC₁₋₁₂alkyl groups. In particular aspects, the second polymer may comprise a repeat unit of the following Formula (3):

wherein in Formula (3) R₄ and R₅ are each independently a hydrogen, a halogen, a C₁₋₈alkyl, or C₁₋₈haloalkyl group such as fluoroC₁₋₈alkyl, and L is an optionally substituted multivalent linking group such as —(CH₂)q- where q is 1, 2, 3, 4, 5, or 6.

In preferred aspects, the additive compound comprises one or more anhydride moieties. Preferred additive compounds also may be halogenated particularly fluorinated. Preferred additive compounds also may comprise a sulfonic acid ester group.

In a further aspect, topcoat compositions for use over a photoresist layer are provided, Preferred topcoat compositions may comprise (a) a first matrix polymer; (b) a second polymer distinct from the first polymer; and (c) one or more additive compounds having a structure of the following Formulae (I) or (II):

wherein in each of those Formulae (I) and (2), R₁, R₂ X, and R₃ and n are the same as defined above.

Preferably, the second polymer of a topcoat composition will comprise fluoro substitution such as one or more fluoroC₁₋₁₂alkyl groups. In particular aspects, the second polymer may comprise a repeat unit of the following Formula (3):

wherein in Formula (3) R₄ and R₅ are each independently a hydrogen, a halogen, a C₁₋₈alkyl, or C₁₋₈haloalkyl group such as fluoroC₁₋₈alkyl, and L is an optionally substituted multivalent linking group such as —(CH₂)q- where q is 1, 2, 3, 4, 5, or 6.

In preferred aspects, the additive compound comprises one or more anhydride moieties. Preferred additive compounds also may be halogenated particularly fluorinated. Preferred additive compounds also may comprise a sulfonic acid ester group.

According to a further aspect, coated substrates are provided. The coated substrates comprise a substrate and a layer of a photoresist composition of the invention over a surface of the substrate. Coated substrates also are provided that comprise a substrate and a layer of a topcoat composition of the invention.

The topcoat composition typically will be coated over a photoresist composition layer, which may be a photoresist composition of the invention.

According to a yet further aspect, methods of forming a photolithographic pattern are provided. The methods suitably comprise: (a) providing a substrate comprising one or more layers to be patterned over a surface of the substrate; (b) applying a layer of a photoresist composition of the invention over the one or more layers to be patterned; (c) patternwise exposing the photoresist composition layer to activating radiation; and (d) applying a developer to the photoresist composition layer to thereby produce a resist relief image. Suitably, the exposed photoresist composition layer is thermally treated in a post-exposure bake process prior to development.

In a preferred aspect, unexposed portions of the photoresist layer are removed by the developer, leaving a photoresist pattern over the one or more layer to be patterned. The patternwise exposing can be conducted by immersion lithography or, alternatively, using dry exposure techniques. In certain aspects, implant and EUV lithography processes are also preferred.

Additional provided methods include forming a photolithographic pattern, comprising: (a) providing a substrate comprising one or more layers to be patterned over a surface of the substrate; (b) applying a layer of a photoresist composition over the one or more layers to be patterned; (c) applying a layer of a topcoat composition of the invention over or above the photoresist composition layer; (d) patternwise exposing both the topcoat composition layer and the photoresist composition layer to activating radiation; and (e) applying a developer to the imaged, coated substrate to thereby produce a resist relief image. Suitably, the exposed photoresist composition and topcoat composition layers are thermally treated in a post-exposure bake process prior to development. In various aspects, patternwise exposing can be conducted by immersion lithography or, alternatively, using dry exposure techniques. In certain aspects, implant and EUV lithography processes are also preferred.

The invention also includes polymers that comprise a reactive nitrogen-containing moiety spaced from the polymer backbone, wherein the nitrogen-containing moiety produces a basic cleavage product during lithographic processing of the photoresist composition.

Electronic devices formed by the disclosed methods are also provided.

Other aspects of the invention are disclosed infra.

DETAILED DESCRIPTION

Preferred additive compounds for use in photoresist and topcoat compositions may be polymeric or non-polymeric, with non-polymeric additive compounds preferred for many applications. Preferred additive compounds have relatively low molecular weight, for example, a molecular weight of less than or equal to 3000, more preferably ≤2500, ≤2000, ≤1500, ≤1000, ≤800 or even more preferably ≤500.

Preferred additive compounds exhibit good solubility n orghanic photoresist solcents such as ethyl lactate, propylene glycol methyl ether acetate (PGMEA), cyclohexanone and mixtures thereof.

In one aspect, preferred are additive compounds that comprise a blocked or masked acid group, such as an anhydride group.

Additive compounds useful in the present invention are generally commercially available or can be readily synthesized. See, for instance, the examples which follow.

Photoresist and topcoat compositions of the invention suitably may comprise one or more additive compounds in a wide amount range, such as from 0.005 to 20 wt. %, based on weight of total solids of the photoresist or topcoat composition (total solids are all composition components except solvent), more preferably in amounts of 0.01, 0.05, 0.1, 0.02, 0.3, 0.4, 0.5 or 1 to 1, 2, 3, 4, 5 or 10 wt % based on total weight total solids of the composition and more typically amounts of 0.01, 0.05, 0.1, 0.02, 0.3, 0.4, 0.05 or 1 to 5, 6, 7, 8, 9 or 10 weight percent.

Specifically preferred additive compounds include the following:

In preferred compositions, the first polymer can migrate toward the upper surface of the resist coating layer during coating of the photoresist composition. In certain systems, this can form a surface layer substantially made up of the first polymer. Without being bound by any theory, the nitrogen (basic) moiety of the first polymer is believed to contribute to the control of scattered or stray light, thereby allowing for reduction in patterning defects such as missing contact holes and micro-bridging defects in the case of line and trench pattern formation. Following exposure and post exposure bake (PEB), the resist coating layer can be developed, including in a developer comprising an organic solvent. The organic developer removes unexposed regions of the photoresist layer and the surface layer of the exposed regions. Benefits of the inventive photoresist compositions can be achieved when using the compositions in dry lithography or immersion lithography processes. When used in immersion lithography, preferred photoresist compositions can further exhibit reduced migration (leaching) of photoresist materials into an immersion fluid also a result of the additive polymer's migration to the resist surface. Significantly, this can be achieved without use of a topcoat layer over the photoresist.

The photoresists can be used at a variety of radiation wavelengths, for example, wavelengths of sub-400 nm, sub-300 or sub-200 nm, or with 248 nm, 193 nm and EUV (e.g., 13.5 nm) exposure wavelengths being preferred. The compositions can further be used in electron beam (E-beam) exposure processes.

The photoresist compositions of the invention are preferably chemically-amplified materials. In preferred embodiments, the photoresist compositions comprise one or more second or matrix polymers (distinct from the first polymer) that comprise an acid labile group. The acid labile group is a chemical moiety that readily undergoes deprotection reaction in the presence of an acid. The second or matrix polymer as part of a layer of the photoresist composition undergoes a change in solubility in a developer described herein as a result of reaction with acid generated from the photoacid and/or thermal acid generator during lithographic processing, particularly following softbake, exposure to activating radiation and post exposure bake. This results from photoacid-induced cleavage of the acid labile group, causing a change in polarity of the second polymer. The acid labile group can be chosen, for example, from tertiary alkyl carbonates, tertiary alkyl esters, tertiary alkyl ethers, acetals and ketals. Preferably, the acid labile group is an ester group that contains a tertiary non-cyclic alkyl carbon or a tertiary alicyclic carbon covalently linked to a carboxyl oxygen of an ester of the second matrix polymer. The cleavage of such acid labile groups results in the formation of carboxylic acid groups. Suitable acid labile-group containing units include, for example, acid-labile (alkyl)acrylate units, such as t-butyl (meth)acrylate, 1-methylcyclopentyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-isopropylcyclopentyl (meth)acrylate, 1-propylcyclopentyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclohexyl (meth)acrylate, 1-isopropylcyclohexyl (meth)acrylate, 1-propylcyclohexyl (meth)acrylate, t-butyl methyladamantyl(meth)acrylate, ethylfenchyl(meth)acrylate, and the like, and other cyclic, including alicyclic, and non-cyclic (alkyl) acrylates. Acetal and ketal acid labile groups can be substituted for the hydrogen atom at the terminal of an alkali-soluble group such as a carboxyl group or hydroxyl group, so as to be bonded with an oxygen atom. When acid is generated, the acid cleaves the bond between the acetal or ketal group and the oxygen atom to which the acetal-type acid-dissociable, dissolution-inhibiting group is bonded. Exemplary such acid labile groups are described, for example, in U.S. Pat. Nos. 6,057,083, 6,136,501 and 8,206,886 and European Pat. Pub. Nos. EP01008913A1 and EP00930542A1. Also suitable are acetal and ketal groups as part of sugar derivative structures, the cleavage of which would result in the formation of hydroxyl groups, for example, those described in U.S. Patent Application No. US2012/0064456A1.

For imaging at wavelengths of 200 nm or greater such as 248 nm, suitable resin materials (including for use as second polymers of the present photoresist compositions) include, for example, phenolic resins that contain acid-labile groups. Particularly preferred resins of this class include: (i) polymers that contain polymerized units of a vinyl phenol and an acid labile (alkyl) acrylate as described above, such as polymers described in U.S. Pat. Nos. 6,042,997 and 5,492,793; (ii) polymers that contain polymerized units of a vinyl phenol, an optionally substituted vinyl phenyl (e.g., styrene) that does not contain a hydroxy or carboxy ring substituent, and an acid labile (alkyl) acrylate such as described above, such as polymers described in U.S. Pat. No. 6,042,997; (iii) polymers that contain repeat units that comprise an acetal or ketal moiety that will react with photoacid, and optionally aromatic repeat units such as phenyl or phenolic groups; such polymers described in U.S. Pat. Nos. 5,929,176 and 6,090,526, and blends of (i) and/or (ii) and/or (iii).

For imaging at certain sub-200 nm wavelengths such as 193 nm, the second or matrix polymer is typically substantially free (e.g., less than 15 mole %), preferably completely free, of phenyl, benzyl or other aromatic groups where such groups are highly absorbing of the radiation. Suitable polymers that are substantially or completely free of aromatic groups are disclosed in European Patent Publication No. EP930542A1 and U.S. Pat. Nos. 6,692,888 and 6,680,159.

Other suitable second or matrix polymers include, for example, those which contain polymerized units of a non-aromatic cyclic olefin (endocyclic double bond) such as an optionally substituted norbornene, for example, polymers described in U.S. Pat. Nos. 5,843,624 and 6,048,664. Still other suitable matrix polymers include polymers that contain polymerized anhydride units, particularly polymerized maleic anhydride and/or itaconic anhydride units, such as disclosed in European Published Application EP01008913A1 and U.S. Pat. No. 6,048,662.

Also suitable as the second or matrix polymer is a resin that contains repeat units that contain a hetero atom, particularly oxygen and/or sulfur (but other than an anhydride, i.e., the unit does not contain a keto ring atom). The heteroalicyclic unit can be fused to the polymer backbone, and can comprise a fused carbon alicyclic unit such as provided by polymerization of a norbornene group and/or an anhydride unit such as provided by polymerization of a maleic anhydride or itaconic anhydride. Such polymers are disclosed in International Pub. No. WO0186353A1 and U.S. Pat. No. 6,306,554. Other suitable hetero-atom group containing matrix polymers include polymers that contain polymerized carbocyclic aryl units substituted with one or more hetero-atom (e.g., oxygen or sulfur) containing groups, for example, hydroxy naphthyl groups, such as disclosed in U.S. Pat. No. 7,244,542.

In the case of sub-200 nm wavelengths such as 193 nm and EUV (e.g., 13.5 nm), the second or matrix polymer may include a unit containing a lactone moiety for controlling the dissolution rate of the second matrix polymer and photoresist composition. Suitable monomers for use in the second or matrix polymer containing a lactone moiety include, for example, the following:

Such a second or matrix polymer further typically includes a unit containing a polar group, which enhances etch resistance of the matrix polymer and photoresist composition and provides additional means to control the dissolution rate of the matrix polymer and photoresist composition. Monomers for forming such a unit include, for example, the following:

The second or matrix polymer can include one or more additional units of the types described above. Typically, the additional units for the second or matrix polymer will include the same or similar polymerizable group as those used for the monomers used to form the other units of the polymer, but may include other, different polymerizable groups in the same polymer backbone.

In preferred aspects, the second or matrix polymer has a higher surface energy than that of the first or additive polymer, described below, and should be substantially non-miscible with the second polymer. As a result of the difference in surface energies, segregation of the second polymer from the first polymer can take place during spin-coating. A suitable surface energy of the second or matrix polymer is typically from 20 to 50 mN/m, preferably from 30 to 40 mN/m.

While not to be limited thereto, exemplary second or matrix polymers include, for example, the following:

As discussed, in preferred aspects, the second polymer may have halogen substitution such as fluoro substitution, including fluoroalkyl, e.g. polymers that have hexofluoropropylalcohol substitution.

Suitable second or matrix polymers for use in the photoresist compositions of the invention are commercially available and can readily be made by persons skilled in the art. The second polymer is present in the resist composition in an amount sufficient to render an exposed coating layer of the resist developable in a suitable developer solution. Typically, the second polymer is present in the composition in an amount of from 50 to 95 wt % based on total solids of the resist composition. The weight average molecular weight M_(w) of the second polymer is typically less than 100,000, for example, from 3000 to 100,000, more typically from 3000 to 15,000. Blends of two or more of the above-described second polymers can suitably be used in the photoresist compositions of the invention.

The first or additive polymer is preferably a material that has a lower surface energy than that of the second polymer and should be substantially non-miscible with the second polymer. In this way, segregation or migration of the first polymer to the top or upper portions of an applied photoresist layer during the coating process is facilitated. While the desired surface energy of the first polymer will depend on the particular second polymer and its surface energy, the first polymer surface energy is typically from 18 to 40 mN/m, preferably from 20 to 35 mN/m and more preferably from 29 to 33 mN/m. While the first polymer migrates to the upper surface of the resist layer during the coating process, it is preferable that there be some intermixing between the first polymer and second or matrix polymer immediately beneath the resist layer surface. Such intermixing is believed to aid in reducing surface inhibition in the resist layer by reduction or elimination of the acid generated in dark regions in the vicinity of the second or matrix polymer due to stray light. The extent of intermixing will depend, for example, on the difference in surface energy (SE) between the second or matrix polymer (MP) and first or additive polymer (AP) (ΔSE=SE_(MP)−SE_(AP)). For given first or matrix and second or additive polymers, the degree of intermixing can be increased with reduced ΔSE. The ΔSE is typically from 2 to 32 mN/m, preferably from 5 to 15 mN/m.

As discussed, the first or additive polymers useful in the photoresist compositions are copolymers that have a plurality of distinct repeat units, for example, two, three or four distinct repeat units.

The first polymer is preferably free of silicon. Silicon-containing polymers exhibit a significantly lower etch rate than organic photoresist polymers in certain etchants. As a result, aggregation of a silicon-containing first polymer at the surface of an organic second polymer-based resist layer can cause cone defects during the etching process. The first polymer may contain fluorine or can be free of fluorine. Preferred first polymers are soluble in the same organic solvent(s) used to formulate the photoresist composition. Preferred first polymers also will be soluble or become soluble upon post exposure bake (e.g., 120° C. for 60 seconds) in organic developers used in negative tone development processes.

As discussed, the first polymer preferably may contain a unit formed from one or more monomer corresponding to the following Formula (I):

X₁—R₁—X₂—R₂—X₃  (I)

wherein X₁ is a polymerizable functional group such as an acrylate or alkylacrylate such as a methacrylate; R₁ may be an optionally substituted linear, branched or cyclic aliphatic group or an aromatic group, suitably C₁₋₁₅ alkyl and optionally fluorinated; X₂ is a basic moiety such as a nitrogen and may be a component of or taken together with R₁ (e.g. R₁ and X₂ may combine to form a piperdinyl moiety); R₂ is an acid labile group; and X₃ may be optionally substituted linear, branched or cyclic aliphatic group or an aromatic group.

The polymerizable functional group X₁ can be chosen, for example, from the following general formulae (P-1), (P-2) and (P-3):

wherein R₂ is chosen from hydrogen, fluorine and fluorinated and non-fluorinated C1 to C3 alkyl; and X is oxygen or sulfur;

wherein R₃ is chosen from hydrogen, fluorine and fluorinated and non-fluorinated C1 to C3 alkyl; and

wherein m is an integer from 0 to 3.

Exemplary suitable monomers are described below, but are not limited to these structures.

Preferably, the first polymer also comprises one or more additional distinct units (second units) formed from monomers corresponding to the following general formula (I-1):

wherein: R₂ is chosen from hydrogen, fluorine and fluorinated and non-fluorinated C1 to C3 alkyl; and X is oxygen or sulfur; and R₄ is chosen from substituted and unsubstituted C1 to C20 linear, branched and cyclic hydrocarbons, preferably fluorinated and non-fluorinated C1 to C15 alkyl, more preferably fluorinated and non-fluorinated C3 to C8 alkyl and most preferably fluorinated and non-fluorinated C4 to C5 alkyl, with R₄ preferably being branched to provide a higher water receding contact angle when used in immersion lithography, and R₄ substitutions of haloalkyl and haloalcohol such as fluoroalkyl and fluoroalcohol being suitable.

As discussed, various moieties of monomers, polymers and other materials may be optionally substituted (or stated to be “substituted or unsubstituted”). A “substituted” substituent may be substituted at one or more available positions, typically 1, 2, or 3 positions by one or more suitable groups such as e.g. halogen (particularly F, Cl or Br); cyano; nitro; C₁₋₈ alkyl; C₁₋₈ alkoxy; C₁₋₈ alkylthio; C₁₋₈ alkylsulfonyl; C₂₋₈ alkenyl; C₂₋₈ alkynyl; hydroxyl; nitro; alkanoyl such as a C₁₋₆ alkanoyl e.g. acyl, haloalkyl particularly C₁₋₈ haloalkyl such as CF₃; —CONHR, —CONRR′ where R and R′ are optionally substituted C₁₋₈alkyl; —COOH, COC, >C═O; and the like.

Exemplary suitable monomers of Formula (I-1) are described below, but are not limited to these structures. For purposes of these structures, “R₂” and “X” are as defined above for Formula I-1.

Exemplary first polymers useful in the present photoresist compositions include the following. For purposes of these structures, “R₂” and “X” are defined as follows: each R₂ is independently chosen from hydrogen, fluorine and fluorinated and non-fluorinated C1 to C3 alkyl; and each X is independently oxygen or sulfur.

The photoresist compositions suitably include a single first polymer, but can optionally include one or more additional first polymers. Suitable polymers and monomers for use in the photoresist compositions are commercially available and/or can readily be made by persons skilled in the art.

The first polymer is typically present in the photoresist composition in a relatively small amount, for example, in an amount of from 0.1 to 10 wt %, preferably from 0.5 to 5 wt %, more preferably from 1 to 3 wt %, based on total solids of the photoresist composition. The content of the first or additive polymer will depend, for example, on the content of acid generator in the photoresist layer, the content of the nitrogen-containing groups in the first polymer, and whether the lithography is a dry or immersion-type process. For example, the first polymer lower limit for immersion lithography is generally dictated by the need to prevent leaching of the resist components. An excessively high first polymer content will typically result in pattern degradation. The weight average molecular weight of the additive polymer is typically less than 400,000, preferably from 3000 to 50,000, more preferably from 3000 to 25,000. Suitable first polymers and monomers for making the first polymers for use in the photoresist compositions of the invention are commercially available and/or can be made by persons skilled in the art.

The photosensitive composition preferably may comprise one or more photoacid generators (PAG) employed in an amount sufficient to generate a latent image in a coating layer of the photoresist composition upon exposure to activating radiation. For example, the photoacid generator will suitably be present in an amount of from about 1 to 20 wt % based on total solids of the photoresist composition. Typically, lesser amounts of the photoactive component will be suitable for chemically amplified resists.

A topcoat composition also may comprise one or more acid generator compounds, including one or more photoacid generator compound and/or one or more thermal acid generator compounds. The PAGs disclosed herein and amounts thereof for use in a photoresist compositions are suitable for a topcoat composition. Relatively small amounts of a PAG is often suitable for a topcoat composition.

Suitable PAGs are known in the art of chemically amplified photoresists and include, for example: onium salts, for example, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, nitrobenzyl derivatives, for example, 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, and 2,4-dinitrobenzyl p-toluenesulfonate; sulfonic acid esters, for example, 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, for example, bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane; glyoxime derivatives, for example, bis-O-(p-toluenensulfonyl)-α-dimethylglyoxime, and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime; sulfonic acid ester derivatives of an N-hydroxyimide compound, for example, N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester; and halogen-containing triazine compounds, for example, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine. One or more of such PAGs can be used.

Suitable solvents for the photoresist and topcoat compositions of the invention include, for example: glycol ethers such as 2-methoxyethyl ether (diglyme), ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; propylene glycol monomethyl ether acetate; lactates such as methyl lactate and ethyl lactate; propionates such as methyl propionate, ethyl propionate, ethyl ethoxy propionate and methyl-2-hydroxy isobutyrate; Cellosolve esters such as methyl Cellosolve acetate; aromatic hydrocarbons such as toluene and xylene; and ketones such as methylethyl ketone, cyclohexanone and 2-heptanone. A blend of solvents such as a blend of two, three or more of the solvents described above also are suitable. The solvent is typically present in the composition in an amount of from 90 to 99 wt %, more typically from 95 to 98 wt %, based on the total weight of the photoresist composition.

Other optional additives for the photoresist compositions include, for example, actinic and contrast dyes, anti-striation agents, plasticizers, speed enhancers, sensitizers, and the like. Such optional additives if used are typically present in the composition in minor amounts such as from 0.1 to 10 wt % based on total solids of the photoresist composition, although fillers and dyes can be present in relatively large concentrations, for example, from 5 to 30 wt % based on total solids of the photoresist composition.

A preferred optional additive of resist compositions of the invention is an added base which can enhance resolution of a developed resist relief image. Suitable basic quenchers include, for example: linear and cyclic amides and derivatives thereof such as N,N-bis(2-hydroxyethyl)pivalamide, N,N-Diethylacetamide, N1,N1,N3,N3-tetrabutylmalonamide, 1-methylazepan-2-one, 1-allylazepan-2-one and tert-butyl 1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarbamate; aromatic amines such as pyridine, and di-tert-butyl pyridine; aliphatic amines such as triisopropanolamine, n-tert-butyldiethanolamine, tris(2-acetoxy-ethyl) amine, 2,2′,2″,2′″-(ethane-1,2-diylbis(azanetriyl))tetraethanol, and 2-(dibutylamino)ethanol, 2,2′,2″-nitrilotriethanol; cyclic aliphatic amines such as 1-(tert-butoxycarbonyl)-4-hydroxypiperidine, tert-butyl 1-pyrrolidinecarboxylate, tert-butyl 2-ethyl-1H-imidazole-1-carboxylate, di-tert-butyl piperazine-1,4-dicarboxylate and N (2-acetoxy-ethyl) morpholine. Of these basic quenchers, 1-(tert-butoxycarbonyl)-4-hydroxypiperidine and triisopropanolamine are preferred. The added base is suitably used in relatively small amounts, for example, from 1 to 20 wt % relative to the PAG, more typically from 5 to 15 wt % relative to the PAG.

The photoresist and topcoat compositions can be used in accordance with the invention are generally prepared following known procedures. For example, a resist of the invention can be prepared as a coating composition by dissolving the components of the photoresist in a suitable solvent, for example, one or more of: a glycol ether such as 2-methoxyethyl ether (diglyme), ethylene glycol monomethyl ether, propylene glycol monomethyl ether; propylene glycol monomethyl ether acetate; lactates such as ethyl lactate or methyl lactate, with ethyl lactate being preferred; propionates, particularly methyl propionate, ethyl propionate and ethyl ethoxy propionate; a Cellosolve ester such as methyl Cellosolve acetate; an aromatic hydrocarbon such toluene or xylene; or a ketone such as methylethyl ketone, cyclohexanone and 2-heptanone. The desired total solids content of the photoresist will depend on factors such as the particular polymers in the composition, final layer thickness and exposure wavelength. Typically the solids content of the photoresist varies from 1 to 10 wt %, more typically from 2 to 5 wt %, based on the total weight of the photoresist composition.

The invention further provides methods for forming a photoresist relief image and producing an electronic device using photoresists of the invention. The invention also provides novel articles of manufacture comprising substrates coated with a photoresist composition of the invention.

In lithographic processing, a photoresist composition may be applied on a variety of substrates. The substrate can be of a material such as a semiconductor, such as silicon or a compound semiconductor (e.g., III-V or II-VI), glass, quartz, ceramic, copper and the like. Typically, the substrate is a semiconductor wafer, such as single crystal silicon or compound semiconductor wafer, and may have one or more layers and patterned features formed on a surface thereof. One or more layers to be patterned may be provided over the substrate. Optionally, the underlying base substrate material itself may be patterned, for example, when it is desired to form trenches in the substrate material. In the case of patterning the base substrate material itself, the pattern shall be considered to be formed in a layer of the substrate.

The layers may include, for example, one or more conductive layers such as layers of aluminum, copper, molybdenum, tantalum, titanium, tungsten, alloys, nitrides or silicides of such metals, doped amorphous silicon or doped polysilicon, one or more dielectric layers such as layers of silicon oxide, silicon nitride, silicon oxynitride, or metal oxides, semiconductor layers, such as single-crystal silicon, and combinations thereof. The layers to be etched can be formed by various techniques, for example, chemical vapor deposition (CVD) such as plasma-enhanced CVD, low-pressure CVD or epitaxial growth, physical vapor deposition (PVD) such as sputtering or evaporation, or electroplating. The particular thickness of the one or more layers to be etched 102 will vary depending on the materials and particular devices being formed.

Depending on the particular layers to be etched, film thicknesses and photolithographic materials and process to be used, it may be desired to dispose over the layers a hard mask layer and/or a bottom antireflective coating (BARC) over which a photoresist layer is to be coated. Use of a hard mask layer may be desired, for example, with very thin resist layers, where the layers to be etched require a significant etching depth, and/or where the particular etchant has poor resist selectivity. Where a hard mask layer is used, the resist patterns to be formed can be transferred to the hard mask layer which, in turn, can be used as a mask for etching the underlying layers. Suitable hard mask materials and formation methods are known in the art. Typical materials include, for example, tungsten, titanium, titanium nitride, titanium oxide, zirconium oxide, aluminum oxide, aluminum oxynitride, hafnium oxide, amorphous carbon, silicon oxynitride and silicon nitride. The hard mask layer can include a single layer or a plurality of layers of different materials. The hard mask layer can be formed, for example, by chemical or physical vapor deposition techniques.

A bottom antireflective coating may be desirable where the substrate and/or underlying layers would otherwise reflect a significant amount of incident radiation during photoresist exposure such that the quality of the formed pattern would be adversely affected. Such coatings can improve depth-of-focus, exposure latitude, linewidth uniformity and CD control. Antireflective coatings are typically used where the resist is exposed to deep ultraviolet light (300 nm or less), for example, KrF excimer laser light (248 nm) or ArF excimer laser light (193 nm). The antireflective coating can comprise a single layer or a plurality of different layers. Suitable antireflective materials and methods of formation are known in the art. Antireflective materials are commercially available, for example, those sold under the AR™ trademark by Rohm and Haas Electronic Materials LLC (Marlborough, Mass. USA), such as AR™40A and AR™124 antireflectant materials.

A photoresist layer formed from a composition of the invention as described above is applied on the substrate. The photoresist composition is typically applied to the substrate by spin-coating. During spin-coating, in resist compositions comprising both first and second polymers as disclosed herein, the first polymer in the photoresist segregates to the upper surface of the formed resist layer typically with intermixing with the second polymer in regions immediately below the upper surface. The solids content of the coating solution can be adjusted to provide a desired film thickness based upon the specific coating equipment utilized, the viscosity of the solution, the speed of the coating tool and the amount of time allowed for spinning A typical thickness for the photoresist layer is from about 500 to 3000 Å.

The photoresist layer can next be softbaked to minimize the solvent content in the layer, thereby forming a tack-free coating and improving adhesion of the layer to the substrate. The softbake can be conducted on a hotplate or in an oven, with a hotplate being typical. The softbake temperature and time will depend, for example, on the particular material of the photoresist and thickness. Typical softbakes are conducted at a temperature of from about 90 to 150° C., and a time of from about 30 to 90 seconds.

A topcoat composition can be utilized in accordance with known procedures and coated over an applied photoresist. See US20170090287 for procedures using a topcoat composition which can be employed for the present topcoat compositions. Suitably, a top coat composition is utilized with an immersion exposure protocol.

The photoresist layer is next suitably exposed to activating radiation through a photomask to create a difference in solubility between exposed and unexposed regions. References herein to exposing a photoresist composition to radiation that is activating for the composition indicates that the radiation is capable of forming a latent image in the photoresist composition. The photomask has optically transparent and optically opaque regions corresponding to regions of the resist layer to remain and be removed, respectively, in a subsequent development step. The exposure wavelength is typically sub-400 nm, sub-300 nm or sub-200 nm, with 248 nm, 193 nm and EUV wavelengths being typical. Photoresist materials can further be used with electron beam exposure. The methods find use in immersion or dry (non-immersion) lithography techniques. The exposure energy is typically from about 10 to 80 mJ/cm², dependent upon the exposure tool and the components of the photosensitive composition.

Following exposure of the photoresist layer, a post-exposure bake (PEB) is performed. The PEB can be conducted, for example, on a hotplate or in an oven. Conditions for the PEB will depend, for example, on the particular photoresist composition and layer thickness. The PEB is typically conducted at a temperature of from about 80 to 150° C., and a time of from about 30 to 90 seconds. A latent image defined by the boundary (dashed line) between polarity-switched and unswitched regions (corresponding to exposed and unexposed regions, respectively) is formed in the photoresist. The basic moiety (e g amine) of the first polymer deprotected during the post-exppsire bake is believed to prevent polarity switch in dark regions of the photoresist layer where stray or scattered light may be present, resulting in a latent image with vertical walls. This is a result of neutralization of acid generated by the PAG in the dark regions. As a result, cleavage of the acid-labile groups in those regions can be substantially prevented.

The exposed photoresist layer is next developed suitably to remove unexposed regions of the photoresist layer. As discussed, the developer may be an organic developer, for example, a solvent chosen from ketones, esters, ethers, hydrocarbons, and mixtures thereof. Suitable ketone solvents include, for example, acetone, 2-hexanone, 5-methyl-2-hexanone, 2-heptanone, 4-heptanone, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone and methyl isobutyl ketone. Suitable ester solvents include, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate and propyl lactate. Suitable ether solvents include, for example, dioxane, tetrahydrofuran and glycol ether solvents, for example, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether and methoxymethyl butanol. Suitable amide solvents include, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide and N,N-dimethylformamide. Suitable hydrocarbon solvents include, for example, aromatic hydrocarbon solvents such as toluene and xylene. In addition, mixtures of these solvents, or one or more of the listed solvents mixed with a solvent other than those described above or mixed with water can be used. Other suitable solvents include those used in the photoresist composition. The developer is preferably 2-heptanone or a butyl acetate such as n-butyl acetate.

Mixtures of organic solvents can be employed as a developer, for example, a mixture of a first and second organic solvent. The first organic solvent can be chosen from hydroxy alkyl esters such as methyl-2-hydroxyisobutyrate and ethyl lactate; and linear or branched C₅ to C₆ alkoxy alkyl acetates such as propylene glycol monomethyl ether acetate (PGMEA). Of the first organic solvents, 2-heptanone and 5-methyl-2-hexanone are preferred. The second organic solvent can be chosen from linear or branched unsubstituted C₆ to C₈ alkyl esters such as n-butyl acetate, n-pentyl acetate, n-butyl propionate, n-hexyl acetate, n-butyl butyrate and isobutyl butyrate; and linear or branched C₈ to C₉ ketones such as 4-octanone, 2,5-dimethyl-4-hexanone and 2,6-dimethyl-4-heptanone. Of the second organic solvents, n-butyl acetate, n-butyl propionate and 2,6-dimethyl-4-heptanone are preferred. Preferred combinations of the first and second organic solvent include 2-heptanone/n-butyl propionate, cyclohexanone/n-butyl propionate, PGMEA/n-butyl propionate, 5-methyl-2-hexanone/n-butyl propionate, 2-heptanone/2,6-dimethyl-4-heptanone and 2-heptanone/n-butyl acetate. Of these, 2-heptanone/n-butyl acetate and 2-heptanone/n-butyl propionate are particularly preferred.

The organic solvents are typically present in the developer in a combined amount of from 90 wt % to 100 wt %, more typically greater than 95 wt %, greater than 98 wt %, greater than 99 wt % or 100 wt %, based on the total weight of the developer.

The developer also may be an aqueous alkaline composition such as a TMAH composition. Aqueous alkaline developers are commercially available.

The developer material may include optional additives, for example, surfactants such as described above with respect to the photoresist. Such optional additives typically will be present in minor concentrations, for example, in amounts of from about 0.01 to 5 wt % based on the total weight of the developer.

The developer is typically applied to the substrate by spin-coating. The development time is for a period effective to remove the unexposed regions of the photoresist, with a time of from 5 to 30 seconds being typical. Development is typically conducted at room temperature. The development process can be conducted without use of a cleaning rinse following development. In this regard, it has been found that the development process can result in a residue-free wafer surface rendering such extra rinse step unnecessary.

The BARC layer, if present, is selectively etched using resist pattern as an etch mask, exposing the underlying hardmask layer. The hardmask layer is next selectively etched, again using the resist pattern as an etch mask, resulting in patterned BARC and hardmask layers. Suitable etching techniques and chemistries for etching the BARC layer and hardmask layer are known in the art and will depend, for example, on the particular materials of these layers. Dry-etching processes such as reactive ion etching are typical. The resist pattern and patterned BARC layer are next removed from the substrate using known techniques, for example, oxygen plasma ashing.

The following non-limiting examples are illustrative of the invention.

EXAMPLES Molecular Weight Determination:

In the following Examples, number and weight-average molecular weights, Mn and Mw, and polydispersity (PDI) values (Mw/Mn) for the polymers were measured by gel permeation chromatography (GPC) on a Waters alliance system equipped with a refractive index detector. Samples were dissolved in HPLC grade THF at a concentration of approximately 1 mg/mL and injected through four Shodex columns (KF805, KF804, KF803 and KF802). A flow rate of 1 mL/min and temperature of 35° C. were maintained. The columns were calibrated with narrow molecular weight PS standards (EasiCal PS-2, Polymer Laboratories, Inc.).

Examples 1-2: Resin Preparation

The following monomers were used to prepare fluorine-containing polymers B1 and B2 as described below.

Example 1: Polymer B1 Synthesis

A monomer feed solution was prepared by combining 139.5 g propylene glycol monomethyl ether acetate (PGMEA), 150.0 g monomer M1, and 30.0 g monomer M2. An initiator feed solution was prepared by combining 59.0 g PGMEA and 4.45 g V-601. The mixtures were agitated to dissolve the components. 167.5 g PGMEA was introduced into a reaction vessel and the vessel was purged with nitrogen for 30 minutes. The reaction vessel was next heated to 80° C. with agitation. The monomer feed solution was then introduced into the reaction vessel and fed over a period of 2 hours, and the initiator feed solution was simultaneously fed into the reaction vessel over a period of 3 hours. The reaction vessel was maintained at 80° C. for an additional seven hours with agitation, and was then allowed to cool to room temperature. The reaction mixture was diluted with 500 mL tetrahydrofuran, then the polymer was precipitated by dropwise addition of the reaction mixture into 10 L of 4/1 methanol/water (v/v). The solid polymer was collected by filtration, and dried in vacuo. Polymer B1 was obtained as a white solid powder [Yield: 143 g, Mw=34.3 kDa, PDI=2.4].

Example 2: Polymer B2 Synthesis

A monomer feed solution was prepared by combining 89.1 g propylene glycol monomethyl ether acetate (PGMEA), 188.0 g monomer M1, and 12.0 g monomer M3. An initiator feed solution was prepared by combining 80.9 g PGMEA and 10.0 g V-601. The mixtures were agitated to dissolve the components. 120.0 g PGMEA was introduced into a reaction vessel and the vessel was purged with nitrogen for 30 minutes. The reaction vessel was next heated to 90° C. with agitation. The monomer feed solution was then introduced into the reaction vessel and fed over a period of 2 hours, and the initiator feed solution was simultaneously fed into the reaction vessel over a period of 3 hours. The reaction vessel was maintained at 90° C. for an additional seven hours with agitation, and was then allowed to cool to room temperature. The reaction mixture was diluted with 500 mL tetrahydrofuran, then the polymer was precipitated by dropwise addition of the reaction mixture into 10 L of 4/1 methanol/water (v/v). The solid polymer was collected by filtration, and dried in vacuo. Polymer B2 was obtained as a white solid powder [Yield: 170 g, Mw=10.3 kDa, PDI=2.2].

Example 3: Photoresist Composition Preparation Resist Components:

The following components were used to prepare resist compositions as described in Table 1 below.

Resist Additives:

The following additives were used to prepare resist compositions as described in Table 1.

Resist Composition Preparation:

Resist compositions were formulated by adding the components above to a solvent system comprising 1/1 by weight of propylene glycol monomethyl ether acetate (PGMEA) and methyl 2-hydroxybutyrate (HBM), in the amounts as described in Table 1. Each mixture was filtered through a 0.2 μm PTFE disk.

TABLE 1 Example and comparative resist compositions. Example Polymer A Polymer B PAG PAG PAG Q Additive C Solvent R1 A1 (100) B1 (4) PAG-1 (13) PAG-2 (3) PAG-3 (5) Q1 (0.5) C1 (0.1) S1 (3500) R2 A1 (100) B1 (4) PAG-1 (13) PAG-2 (3) PAG-3 (5) Q1 (0.5) C2 (0.1) S1 (3500) R3 A1 (100) B1 (4) PAG-1 (13) PAG-2 (3) PAG-3 (5) Q1 (0.5) C3 (1) S1 (3500) R4 A1 (100) B1 (4) PAG-1 (13) PAG-2 (3) PAG-3 (5) Q1 (0.5) C4 (0.1) S1 (3500) R5 A1 (100) B2 (4) PAG-1 (13) PAG-2 (3) PAG-3 (5) Q1 (0.5) C1 (0.1) S1 (3500) R6 A1 (100) B2 (4) PAG-1 (13) PAG-2 (3) PAG-3 (5) Q1 (0.5) C2 (0.1) S1 (3500) R7 A1 (100) B2 (4) PAG-1 (13) PAG-2 (3) PAG-3 (5) Q1 (0.5) C3 (0.1) S1 (3500) R8 A1 (100) B2 (4) PAG-1 (13) PAG-2 (3) PAG-3 (5) Q1 (0.5) C4 (0.1) S1 (3500) CR1 A1 (100) B1 (4) PAG-1 (13) PAG-2 (3) PAG-3 (5) Q1 (0.5) S1 (3500) CR2 A1 (100) B1 (4) PAG-1 (13) PAG-2 (3) PAG-3 (5) Q1 (0.5) CX1 (1) S1 (3500) CR3 A1 (100) B1 (4) PAG-1 (13) PAG-2 (3) PAG-3 (5) Q1 (0.5) CX2 (1) S1 (3500) CR4 A1 (100) B1 (4) PAG-1 (13) PAG-2 (3) PAG-3 (5) Q1 (0.5) CX3 (1) S1 (3500) CR5 A1 (100) B2 (4) PAG-1 (13) PAG-2 (3) PAG-3 (5) Q1 (0.5) CX4 (1) S1 (3500) CR = comparative examples; S1 = 1/1 PGMEA/HBM.

Example 4: Resist Evaluations NMR Experiments:

Resist compositions were stored at 35° C. for a specified time, whereupon they were diluted by half with d₆-acetone and ¹⁹F NMR spectra were collected to determine the percent degradation of fluorine-containing polymer B. This was done by comparing integrations of fluorine peak corresponding to polymer and fluorine peak corresponding to degradation product. ¹⁹F NMR spectra were acquired on a Bruker AVANCE III HD 600 MHz spectrometer with a 5 mm SMARTProbe™ at 26° C. All NMR spectra are processed using MestReNova 6.2.1. Data from the analysis is tabulated in Table 2.

TABLE 2 Degradation data from NMR analysis for example and comparative resist compositions. % degradation % degradation % degradation Example Week 0 Week 1 Week 2 BTFIB (R3) 0 0 0 Control (CR1) 1 8 12 BTIB (CR2) 1 10 14 Succinic (CR4) 1 4 10

Shelf Life Stability Experiments:

Resist compositions were stored at 35° C. for a specified time, whereupon they were tested for receding contact angle and lithographic performance.

Receding Contact Angle (RCA) Measurement:

On a TEL ACT-8 track, 200 mm silicon wafers were primed with hexamethyldisilazane (HMDS) at 120° C. for 30 seconds. Resist compositions were coated to a thickness of 1,000 Å using a soft-bake of 85° C. for 60 seconds. Receding water contact angles were measured using a Kruss contact angle goniometer using deionized, Millipore filtered water. For receding contact angle measurement, the droplet size of DI water was 50 μl, and the wafer stage tilting rate was 1°/sec.

Lithographic Processing:

Resist compositions were evaluated by lithography as follows. A 200 mm wafer was first spin-coated with XU080538AA underlayer and baked at 240° C. for 60 seconds to form a 135 nm film. A SiARC was then spin-coated on top and baked at 240° C. for 60 seconds to form a 22 nm film. Finally, the resist composition was spin-coated on top to form a 100 nm film and soft baked at 85° C. for 60 seconds. The coated wafer was then exposed with ArF excimer laser (193 nm) through a mask pattern having dense spaces using an ArF exposure apparatus ASML-1100, NA=0.75 under conventional illumination. Thereafter, the wafer was baked at 95° C. for 60 seconds followed by development with 0.26N aqueous tetramethylammonium hydroxide (TMAH) solution and subsequent water wash. Critical dimensions (CD) was determined by processing the image captured by top-down scanning electron microscopy (SEM) using a Hitachi 9380 CD-SEM, operating at an accelerating voltage of 800 volts (V), probe current of 8.0 picoampereres (pA), using 200K× magnification. A 100 nm dense trench was targeted with a mask CD of 100 nm and 200 nm pitch. 63 sites were averaged for determination of CD.

TABLE 3 Performance data for example and comparative resist compositions. RCA RCA RCA CD CD CD RCA Week 2/ Week 3/ Week 4/ CD Week 2/ Week 3/ Week 4/ Example Week 0 35 C. 35 C. 35 C. Week 0 35 C. 35 C. 35 C. PFP anhydride 92 90 92 92 93 91 (R1) HFB anhydride 92 91 90 94 93 91 (R2) BTFIB (R3) 89 89 89 Koser (R4) 92 86 87 96 95 95 PFP anhydride 90 89 89 91 91 89 (R5) HFB anhydride 88 87 88 91 91 90 (R6) BTFIB (R7) 89 87 87 94 94 92 Koser (R8) 87 83 84 95 95 93 Control (CR1) 87 76 72 97 97 95 BTIB (CR2) 76 71 Acetic (CR3) 89 79 Maleic anhydride 86 84 84 76 94 97 96 (CR5)

Example 5: Topcoat Compositions

An overcoat or topcoat composition of the invention is prepared by admixing the following components, 5.14 g polymer-B solution (20%) in IBIB, 2.21 g Quencher-A solution (1%) in IBIB and 92.7 g IBIB and then this mixture was filtered with a 0.2 micron Nylon filter.

Example 6: Immersion Lithography

300 mm HMDS-primed silicon wafers were spin-coated with ARTM26N (Rohm and Haas Electronic Materials) to form a first bottom anti-reflective coating (BARC) on a TEL CLEAN TRAC LITMUS i+, followed by the hake process for 60 seconds at 205° C.

A coating layer of the photoresist composition of Example 3 (Resist R2) is spin coated over the BARC layer. The topcoat composition of Example 5 is spin coated onto a silicon wafer having a coating layer of the photoresist composition of Example 3 (Resist R2).

The fabricated films are then exposed through a mask on Nikon S306C ArF immersion scanner using the illumination conditions as follows: 1.3 NA, Annular with XY-polarization, δ0.64-0.8 The exposure dose i varied from 23.0 mJ/cm² to 47.0 mJ/cm² by 1 mJ/cm². The exposed film is then post-exposure baked at 90° C. for 60 seconds, followed by developing with 0.26N TMAH aqueous developer. 

1. A photoresist composition comprising: (a) a first matrix polymer; (b) one or more acid generators; and (c) one or more additive compounds having a structure of the following Formulae (I) or (II):

wherein in each of those Formulae (I) and (2) R₁ and R₂ are each the same or different non-hydrogen substituent; X in each formulae is one of the following:

wherein R₃ is a non-hydrogen substituent; and each n is a positive integer of 1 to
 5. 2. The photoresist composition of claim 1 further comprising a second polymer distinct from the first polymer.
 3. The photoresist composition of claim 2 wherein the second polymer is fluorinated.
 4. The photoresist composition of claim 2 wherein the second polymer comprises a repeat unit of the following Formula (3):

wherein in Formula (3) R₄ and R₅ are each independently a hydrogen, a halogen, a C₁₋₈alkyl, or C₁₋₈ haloalkyl group, and L is an optionally substituted multivalent linking group.
 5. The photoresist composition of claim 1 where the additive is an anhydride.
 6. A topcoat composition for use with an overcoated photoresist, the topcoat composition comprising: (a) a first matrix polymer; (b) a second polymer distinct from the first polymer; and (c) one or more additive compounds having a structure of the following Formulae (I) or (II):

wherein in each of those Formulae (I) and (2) R₁ and R₂ are each the same or different non-hydrogen substituent; X in each formulae is one of the following:

wherein R₃ is a non-hydrogen substituent; and each n is a positive integer of 1 to
 5. 7. The topcoat composition of claim 6 wherein the second polymer is fluorinated.
 8. The topcoat composition of claim 7 wherein the second polymer comprises a repeat unit of the following Formula (3):

wherein in Formula (3) R₄ and R₅ are each independently a hydrogen, a halogen, a C₁₋₈alkyl, or C₁₋₈ haloalkyl group, and L is an optionally substituted multivalent linking group.
 9. The topcoat of claim 6 where the additive is an anhydride.
 10. A method for forming a photolithographic pattern, comprising: (a) applying a layer of a photoresist composition of claim 1 on a substrate; (b) patternwise exposing the photoresist composition layer to activating radiation; and (c) developing the exposed photoresist composition layer to provide a photoresist relief image.
 11. A method for processing a photoresist composition, comprising: (a) applying a layer of a photoresist composition on a substrate; (b) above the photoresist composition layer, applying a layer of a composition of claim 6 to form a topcoat layer; (c) patternwise exposing the topcoat layer and photoresist layer to activating radiation; and (d) developing the exposed photoresist composition layer to provide a photoresist relief image. 